Process for the synthesis of unsaturated petroleum hydrocarbon oils



- Patented Jana-I4, 1941 I PATENT oFFicE- UNSAT- URATED PETROLEUM HYDRQCARBON oms Herman B. Kipper, Accord, Mass.

No Drawing. Application May 29, 1939, -seris no..z7t,412

3 Claims.

In patent application, Serial Number 561,158 of September 4th, 1931, which was allowed but abandoned by me, the following description of processing for the production of unsaturated hy- 5 drocarbons from more saturated ones occurs.

I have found that it is possible partially to oxidize hydrocarbons by the use of oxygen, in

other words to oxidize the hydrogen to formwater without oxidation of the carbon content of the molecule. I

In order to carry out the experimental runs, a highv pressure resistant cylinder was filled with nitrogen gas at about fifty to seventy pounds pressure per square inch. A pump circulated this gas, to which oxygen was added in the desired percentage, at the rate of about one liter per minute (at fifty to seventy pounds pressure). I through a heated reaction chamber through which the hydrocarbons were also circulated. Two seriesof experimental runs" were made. -In the first runs, the hydrocarbons were circulated through the reaction chamber at the rate of five grams per minute, whereas oxygen was mixed with the circulating nitrogen in such percentage that approximately .3 of a gram per minute of said oxygen was circulated. The pressure in the reaction chamber was fifty pounds and the temperature thereof 375 degrees C. In twenty minutes 100 grams of hydrocarbons and 6 grams of oxygen had been circulated. The resulting products, including, among others, oxidized hydrocarbon and HzQ; showed a 2% carbon dioxide (CO2) yield. 1

In the second series of runs the percentage 35 of oxygen was increased so that 1' gram per minute thereof was circulated with the 5 grams of hydrocarbon and with the nitrogen at the same pressure and temperature in the reaction chamber. In twenty minutes 20 grams of oxygen .was circulated. The resulting products showed a 7% carbon dioxide yield.

In each case the contents of the gas reaction chamber, pumps, reservoir, etc., approximated 22.4 liters, or practically the volume occupied by one#gram-molecular-weight oi gas at normal pressure. Since the final pressure in each case was about 60 pounds, approximately 4 moles of gas were in the reaction chamber pumps etc., at the end of each run." One molecule 00: weighs 44 grams 2% x44 grams 4 moles=3.5 gms.'COz 7%)(44 grams 4 moles=l2.3 gms. C02

. Respectively, therefore, in the two runs 3.5 55 gm. of CO: and 12.3 gms. of CO: were formed.

Since, in all, in the first run 6 grams of oxygen was grams of oxygen was used, the percentage of oxygen used to'form the respective amount of CO2 is as follows:

X =0.42 or 42% and v I 32 12.5 EXW=OA5 01 45% Thus, about 42-45% of the oxygen used combined with carbon at the above temperature of operation, whereas, excluding a very small percentage, a matter of a few tenths percentage of oxygen found in the residual gas, the greater percentage, or let us say about 58%, with the hydrogen. If each atom of carbon in the hydrocarbon molecule had combined with it originally two atoms of hydrogen, which in turn would combine with half a molecule of oxygen, the total oxygen used for oxidizing the carbon atom and hydrogen atom combined with it should be raised 50% or to a total of 21%. Thus, with a CH: group of the hydrocarbons Ii we consider the carbon atom as having'3 atoms of hydrogen combined with it, the above figures would be, of course, somewhat altered; for instance li /2% more oxygen would combine with the CH2 group /2 of 21%=10 In other words, about 26 /295 (100-42-31 /2) in the .CH: group to 37% (100-42-21) in the CH3 group, of the oxygen utilized acted'selectively to oxidize the hydrogen. At 200 to 300 degrees 0., practically all of the oxygen used acted selectively, no carbon-dioxide, or at most only a few tenths percent (this small percentage might well be within the limits of error of my analytical method) were found in the residual gas.

The catalytic'materials used were a mixture of finely divided copper and iron oxides with asbestos as the carrier, the preferred catalytic combination being made up of the above oxides secured by aqueous alkaline precipitation of their hydrates from their soluble sulphates in equimolecular proportions, with suitable washing and drying of the hydrates to produce the pure oxides.

Applicant since establishing the above research has done nothing with the processing commercially. One further improvement has been made since the findings described were established. The ferric and cupric oxides usedas catalysts were mixed with anhydrous cupric chloride and combined used and in the second run 20 heated to above five hundred degrees centigrade. The copper chloride is thereby melted and on allowing to cool a solid'formed catalyst is produced. The advantage in use of such catalyst depends on the fact that it is not mechanically carried out of the reaction chamber by the oil as it passes through the said chamber. About seventy-five grams of each of the copper and iron oxides were mixed with three hundred grams oi copper chloride and about fifty grams of asbestos fibre. A tiny percentage of glue was found satisfactory for temporarily binding the mass which was formed into short cylindrical forms in a mold under compression. Subsequently the compressed cylinders were heated as above noted and allowed to cool to give the catalytic mass in the shape of such short cylinders. Of course, balls or other shapes could be somewhat similarly produced.

Applicant believes, from the cases cited, that he was the inventor of the processing basically described and is now duly entering new application to this specific portion of the original application. 7

Applicant was unsuccessful in establishing his results when using air, that is, with a percentage of about twenty percent oxygen to eighty percent nitrogen. The success of all his findings depend on the use of oxygen of a percentage 01' fifteen percent or under to eighty-five percent or more of the inert gas.

I claim:

1. In a process for the dehydrogenation of liquid petroleum hydrocarbons; the step of sub- .iecting the said hydrocarbon oils in the liquid phase to treatment with a mixture 01. oxygen and an inert gas in which the percentage of oxygen in said mixture is less than twenty. namely that normally contained in air, at one hundred and fifty to three hundred and seventy-five degrees centigrade and superatmospheric pressures in the presence of cupric and ferric oxides as catalytic materials.

2. In a process for the dehydrogenation of liquid petroleum hydrocarbons, the step of subjecting the said hydrocarbon oils in the liquid phase to treatment with a mixture of oxygen and an inert gas in which the percentage of oxygen in said mixture is less than twenty, namely that normally contained in air, at one hundred and fifty to three hundred and seventy-five degrees centigrade and superatmospheric pressures in the presence of cupric and ferric oxides, supported on asbestos fibre, as catalytic materials.

3. In a process for the dehydrogenation of liquid petroleum hydrocarbons. the step or subjecting the said hydrocarbon oils in the liquid 1 phase at about seventy pounds pressure and from one hundred and fli'ty to three hundred and seventy-five degrees centigrade, to treatment with a gas mixture containing about seven percent of oxygen mixed with ninety-three percent oi nitrogen in the presence of cupric and ferric oxides, supported on asbestos fibre, as catalytic materials.

HERMAN B. KIPPER. 

